CN1202061C - Method for catalytic synthesising dimethyl ether in combined bed - Google Patents
Method for catalytic synthesising dimethyl ether in combined bed Download PDFInfo
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- CN1202061C CN1202061C CN 02136724 CN02136724A CN1202061C CN 1202061 C CN1202061 C CN 1202061C CN 02136724 CN02136724 CN 02136724 CN 02136724 A CN02136724 A CN 02136724A CN 1202061 C CN1202061 C CN 1202061C
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Abstract
The present invention discloses a method for catalyzing and synthesizing dimethyl ether (DME for short) in a combined bed, which mainly comprises: under reaction conditions, raw gas containing CO, CO2 and H2 (such as raw gas using coal as raw materials, raw gas using natural gas as raw materials, etc.) carries out catalyzing and synthesizing reaction through a reaction device formed by the combination of a three-phase slurry bed and a fixing bed, and thus, the DME can be efficiently synthesized, wherein the total carbon conversion rate can reach 85%, and the selectivity of the DME can reach 95%.
Description
Technical field
The present invention relates to the production method of dme (Dimethyl ether, be called for short DME), particularly relate to a kind of in combination cot the method for catalytic synthesising dimethyl ether.
Background technology
As everyone knows, dme is a kind of ideal clean fuel, can be used as domestic fuel, alcohol-ether fuel and automobile fuel; Be the substitute of Chlorofluorocarbons (CFCs), to reduce destruction to atmospheric ozone layer; It also is the intermediate of some Chemicals.
At present, the industrial process of dme has:
(1) obtain by the by-product that separates in the synthesizing methanol production, because this method output is lower, the industrial application of progressively fading out.
(2) patent CN1111231A has reported the dimethyl ether by methanol dehydration method, patent CN1125216A has reported the technology of gas-phase methanol dewatering preparing dimethy ether, though described method is simple, but reaction is carried out in two steps, the first step is produced methyl alcohol, the second step producing dimethyl ether by dehydrating methanol, technical process is long, and is less economical.
(3) patent CN1285340A discloses the method for dimethyl ether synthesis in three-phase slurry bed, this genealogy of law the present patent application people's a innovation, it has solved the technical barrier of the constant temperature method in the dimethyl ether synthesis process, but unstripped gas all is the laboratory simulation preparation, when it in the face of with the coal being the synthetic gas of raw material production or when being the synthetic gas of raw material production with the natural material, the transformation efficiency of its total carbon is on the low side (less than 60%), the selectivity of DME is less than 80% also, this can be from the embodiment 2 of its disclosed specification sheets, just can be clear that this phenomenon in 3, therefore require further improvement, could satisfy the requirement of branch of industry.
(4) patent application CN1172468A discloses a kind of " preparation method of fuel grade dimethyl ether ", it has made improvement to the production method of " fuel grade dimethyl ether ", but total efficiency of carbon conversion of this method lower (only being 30～50%), the selectivity of DME also not high (only being 73～76%), the ratio of unreacted synthesis gas that the phase cross-demand loops back receipts is very big, be 4～5 times of unstripped gas, so huge logistics makes the input of catalytic unit and catalyzer very big, add a series of inputs such as follow-up refrigerating unit, shown the very poor weakness of this method economy.
In a word, the method for present various production DME all can not satisfy the requirement of branch of industry, has only by further innovation, change, could promote the technical progress that dme is produced in industry.
Summary of the invention
The object of the present invention is to provide a kind of in combination cot the method for catalytic synthesising dimethyl ether, can further improve the utilization ratio of carbon in the synthetic gas, after making synthetic gas pass through the catalytic reaction layer of this combination cot, its total efficiency of carbon conversion is up to more than 70%, the DME transformation efficiency is up to more than 85%, thereby overcomes the shortcoming of prior art preferably.
Design of the present invention is such:
Selecting a kind ofly has higher optionally catalyzer to dimethyl ether synthesis, place the catalyst reaction device that combines by three-phase slurry bed and fixed bed, according to ordinary method to catalyzer reduce handle after, the unstripped gas that mainly contains CO, CO2 and H2 is fed in the slurry-bed reaction section of built-in inert media, form a kind of three-phase bubbling slurry bed, unstripped gas passes the surface of the solid catalyst of inert media arrival suspension and carries out catalyzed reaction, and unreacted unstripped gas enters with the product that reacts generation again and further carries out catalyzed reaction in the fixed bed.
The present invention is divided into two portions up and down with reactor: the bottom is tower or the three-phase slurry bed conversion zone of still formula, and catalyzer is suspended in the inert solvent, and catalyst grain size is 0.1～0.2mm; Top is the fixed bed reaction section, places same catalyzer, but catalyst grain size is φ 5mm * 5mm.Be provided with heat-exchanger rig in the reactor, this device places the reactor of being made up of slurry bed and fixed bed, to remove a large amount of reaction heat that produce in the reaction process.Bottom at reactor is provided with gas distributor; Tripping device (liquid phase that prevents the bottom bed is carried secretly by gas phase and entered the top bed) is set between two reaction beds, and the top is the product outlet.
Unstripped gas carries out building-up reactions at catalyst surface by following equation:
Because CO, CO
2And H
2Synthetic DME is a strong exothermal reaction, CO, H in unstripped gas
2When concentration is higher, if adopt fixed-bed reactor, very easily cause catalytic bed because of the excessive temperature runaway of temperature rise (causing catalyst deactivation), therefore the present invention is provided with three-phase slurry bed conversion zone at reactor lower part, because the thermal capacitance of liquid phase inert solvent is bigger, thereby in the three-phase bed, realize constant temperature method easily, and be suitable for the synthetic gas operation of high CO concentration; And granules of catalyst surface surrounded by solvent, ties the charcoal phenomenon and greatly alleviates.But reactant need be by behind the liquid phase inert media in the three-phase bed, just can enter catalyst surface and carry out catalyzed reaction, speed of reaction is had certain restraining effect, and reaction can not reach high transformation efficiency, so the present invention is provided with the fixed bed reaction section on the top of reactor; In fixed bed because from three-phase slurry bed unreacted CO, CO
2And H
2, its concentration is lower, can directly contact with catalyzer to carry out building-up reactions, and the reaction heat of its generation is removed by heat-exchanger rig, has realized fixed bed operation in controlled range more satisfactoryly, and has reached higher transformation efficiency and selectivity.
According to above-mentioned design, realize that technical scheme of the present invention is as follows:
By with the coal be raw material or with the Sweet natural gas be raw material produce mainly contain CO, CO
2And H
2Unstripped gas, through being preheated to 80～180 ℃, enter then finished that catalyst reduction is handled and filling the combination type reactor bottom of inert liquid phase medium, during promptly tower or still formula is three-phase bubbling slurry bed.The service temperature of lower reaction section (or lower reaction section of reactor) is at 220～280 ℃, and pressure is at 3.0～7.0MPa, and air speed is 1000～15000h
-1Unreacted CO, CO
2And H
2, and (the CH of reaction generation
3)
2O, CH
3OH, H
2O enters in the tower fixed bed again, and promptly in the upper reaction section of reactor, its service temperature is at 220～280 ℃, and pressure is at 3.0～7.0MPa, and air speed is 1000～15000h
-1, the reaction heat that produces in the reaction process is in time removed by the heat-exchanger rig that is arranged in the reaction bed, to keep the stable operation of reaction bed.
Said reactor its underpart is three-phase bubbling slurry bed conversion zone, and top is the fixed bed reaction section, and unstripped gas reacts through two-stage catalytic, makes total efficiency of carbon conversion reach 85%, and the selectivity of DME can reach more than 95%.
Said catalyzer is home-made catalyst for synthesizing copper based methanol and the composite catalyst that improves the molecular sieve composition, and catalyst for synthesizing copper based methanol is (0.4～2.0) with the quality proportioning of improving molecular sieve catalyst: 1, and best proportioning is (0.6～1.5): 1.In three-phase slurry bed, the granularity of catalyzer is 0.1～0.2mm; Catalyst grain size is φ 5mm * 5mm in fixed bed.If with the coal is that the synthetic gas that raw material makes is made unstripped gas, total efficiency of carbon conversion is 65～85%, and the selectivity of DME is 85～95%; Make unstripped gas as if the synthetic gas that with the Sweet natural gas is raw material production, total efficiency of carbon conversion is 60～75%, and the selectivity of DME is 80～90%.
Said inert liquid medium is a medical liquid paraffin, and its initial boiling point is greater than 284 ℃, and sulphur content is less than 0.12mg/L, and detections such as chlorine, arsenic content do not go out.
When dme output was little, it was the three-phase bubbling slurry bed conversion zone of still formula that reactor can adopt the bottom, and top is the combined reaction unit of fixed bed reaction section, and inside can be provided with cold pipe and remove reaction heat.
When dme output was big, it was tower three-phase bubbling slurry bed conversion zone that reactor should adopt the bottom, and top is the fixed bed reaction section, totally is the reaction unit of a cylindrical barrel body, built-in heat exchanger, and the time remove reaction heat.The lower inlet of reactor is provided with gas distributor, and the intersegmental skimming baffle that is provided with can stop the liquid phase solvent of lower reaction section to be entrained into upper reaction section, and the reaction product of the synthetic gained of catalysis is discharged by tower top outlet.
Obviously the method for the present invention's catalytic synthesising dimethyl ether in combination cot also can independently be provided with three-phase bubbling slurry bed reactor and tower fixed-bed reactor respectively, and the centre couples together the fixed-bed reactor of connecting behind the promptly three-phase bubbling slurry bed reactor with pipeline.In a word, without applicant's permission, according to design of the present invention, the method for implementing the synthetic DME of catalysis all constitutes infringement act.
Illustrate content of the present invention below in conjunction with accompanying drawing:
Fig. 1 is a kind of full scale plant synoptic diagram of built-up type catalytic synthesising dimethyl ether.
As seen from Figure 1, the device of realization said method comprises shell of reactor 1, heat exchanger 5, gas distributor 8 and drum 12; Heat exchanger 5 is arranged in the combination cot reactor, and gas distributor 8 is arranged on the bottom of reactor, separator 10 be arranged on three-phase slurry bed 2 and fixed bed 6 between, drum 12 is connected with heat exchanger 5 by pipeline. (granularity 0.1～0.2mm), unstripped gas enter in three-phase slurry bed 2 with bubble 4 forms by gas distributor 8 first at three-phase slurry bed 2 built-in inert liquid mediums 9 and catalyst 3; At fixed bed 6 apparatus with catalyst inside 7 (φ 5mm * 5mm) on sieve plate 11. (all the other supplementary structures are omitted).
During operation, then unstripped gas enters in three-phase slurry bed 2 with bubble 4 forms by gas distributor 8 first through being preheated to 80～180 ℃. Contact with catalyst 3 by inert liquid medium 9 and to carry out catalytic synthesis, reaction heat is then in time removed by heat exchanger 5, unreacted CO, CO2And H2, and (the CH of reaction generation3)
2O、CH
3OH、H
2O again by separator 10, except behind the inert liquid medium of deentrainment, enters in the fixed bed 6, directly contacts with catalyst 7 and carries out catalytic reaction, can obtain high conversion ratio and selective, and reaction heat is removed by heat exchanger 5 equally. The product (comprising DME and methyl alcohol etc.) that reaction generates is discharged by the reactor head outlet.
The said method and apparatus of the present invention has very significant advantage: most of CO, CO in the unstripped gas2And H2Catalyzed and synthesized by three-phase slurry bed conversion zone and to be product, a small amount of unreacted CO, CO2And H2, and (the CH of reaction generation3)
2O、CH
3OH、H
2O enters the fixed bed reaction section again and carries out catalytic reaction, thereby has further improved the selective of total efficiency of carbon con version and DME. When the synthesis gas that makes take coal as raw material was done unstripped gas, what its total efficiency of carbon con version can reach 85%, DME selectively can reach 95%, and when the synthesis gas that makes take natural gas as raw material during as unstripped gas, what its total efficiency of carbon con version can reach 75%, DME selectively can reach 90%; And in controlled range, realized constant temperature method, be conducive to suitability for industrialized production.
The invention will be further described below in conjunction with embodiment:
Embodiment 1
In the autoclave of 500mL, pack into the medical liquid paraffin of 250mL, 7.5 (granularity is 0.125～0.200mm) for gram catalyst for synthesizing copper based methanol and 7.5 gram modified molecular sieve catalysts, φ a 25 * 3mm simultaneously connects, the cylindric fixed-bed reactor of long 615mm, in put 7.5 the gram catalyst for synthesizing copper based methanol and 7.5 the gram modified molecular sieve catalysts (granularity is that φ 5mm * 5mm), after method was routinely reduced, it was as follows to change reaction conditions over to:
220～280 ℃ of temperature of reaction, reaction pressure 3.0～7.0MPa, the inlet gas flow under the normal conditions: 30～45L/h, inlet gas is for being the synthetic gas that raw material makes with the coal, it consists of: CO 28%, H
268%, CO
23%, rare gas element 1%, total efficiency of carbon conversion is 65～85%, the selectivity of DME is 85～95%, detailed being shown in Table 1.
By the content of table 1 and embodiment 1 record as seen:
When the mass ratio of the molecular sieve catalyst of copper base catalyst for methanol and modification is 1; When the volume ratio between slurry bed catalyst reaction section volume and the fixed bed catalyst section is 500/175=10/3.5; Temperature of reaction is that 220～280 ℃, reaction pressure are that the flow of the inlet unstripped gas under 3.0～7.0MPa, the normal conditions is when being 30～45L/h; When inlet gas is the synthetic gas (unstripped gas) that raw material makes with the coal, it consists of: CO 28%, H
268%, CO
23%, during rare gas element 1%, write down the reaction result of whole experiment: total efficiency of carbon conversion is 65～85%, and the selectivity of DME is 85～95%.
In the autoclave of 500mL, pack into the medical liquid paraffin of 250mL, 7.5 (granularity is 0.125～0.200mm) for gram catalyst for synthesizing copper based methanol and 7.5 gram modified molecular sieve catalysts, φ a 25 * 3mm simultaneously connects, the cylindric fixed-bed reactor of long 615mm, in put 7.5 the gram catalyst for synthesizing copper based methanol and 7.5 the gram modified molecular sieve catalysts (granularity is that φ 5mm * 5mm), after method was routinely reduced, it was as follows to change reaction conditions over to:
220～280 ℃ of temperature of reaction, reaction pressure 3.0～7.0MPa, the inlet gas flow 30～45L/h under the normal conditions, inlet gas is for being the unstripped gas that raw material makes with the Sweet natural gas, it consists of: CO 13%, H
270%, CO
213%, rare gas element 4%, total efficiency of carbon conversion is 60～75%, the selectivity of DME is 80～90%, detailed being shown in Table 2.
By the content of table 2 and embodiment 2 records as seen:
When the mass ratio of the molecular sieve catalyst of copper base catalyst for methanol and modification is 1; When the volume ratio between slurry bed catalyst reaction section volume and the fixed bed catalyst section is 500/175=10/3.5; Temperature of reaction is that 220～280 ℃, reaction pressure are that the flow of the inlet unstripped gas under 3.0～7.0MPa, the normal conditions is when being 30～45L/h; When inlet gas is the synthetic gas (unstripped gas) that raw material makes with the coal, it consists of: CO 13%, H
270%, CO
213%, during rare gas element 4%, write down the reaction result of whole experiment: total efficiency of carbon conversion is 60～75%, and the selectivity of DME is 80～90%.
Embodiment 3:
In the autoclave of 500mL, pack into the medical liquid paraffin of 250mL, 7.5 (granularity is 0.125～0.200mm) for gram catalyst for synthesizing copper based methanol and 7.5 gram modified molecular sieve catalysts, φ a 25 * 3mm simultaneously connects, the cylindric fixed-bed reactor of long 615mm, in put 6 the gram catalyst for synthesizing copper based methanol and 9 the gram modified molecular sieve catalysts (granularity is that φ 5mm * 5mm), after method was routinely reduced, it was as follows to change reaction conditions over to:
220～280 ℃ of temperature of reaction, reaction pressure 3.0～7.0MPa, the inlet gas flow 30～45L/h under the normal conditions, inlet gas is for being the unstripped gas that raw material makes with the Sweet natural gas, it consists of: CO 13%, H
270%, CO
213%, rare gas element 4%, total efficiency of carbon conversion is 56～72%, the selectivity of DME is 75～85%, detailed being shown in Table 3.
By the content of table 3 and embodiment 3 records as seen:
When the mass ratio of the molecular sieve catalyst of fixed bed copper base catalyst for methanol and modification becomes 0.67; When the volume ratio between slurry bed catalyst reaction section volume and the fixed bed catalyst section is 500/175=10/3.5; Temperature of reaction is that 220～280 ℃, reaction pressure are that the flow of the inlet unstripped gas under 3.0～7.0MPa, the normal conditions is when being 30～45L/h; When inlet gas is the synthetic gas (unstripped gas) that raw material makes with the coal, it consists of: CO 13%, H
270%, CO
213%, during rare gas element 4%, write down the reaction result of whole experiment: total efficiency of carbon conversion is 56～72%, and the selectivity of DME is 75～85%.
Table 1
| Temperature ℃ | Pressure MPa | Flow L/h | Total efficiency of carbon conversion % | DME selectivity % |
| 220 | 3 | 30 | 65 | 85 |
| 240 | 4 | 45 | 72 | 88 |
| 250 | 5 | 45 | 83 | 91 |
| 250 | 7 | 30 | 85 | 95 |
| 280 | 7 | 45 | 82 | 90 |
Table 2
| Temperature ℃ | Pressure MPa | Flow L/h | Total efficiency of carbon conversion % | DME selectivity % |
| 220 | 3 | 30 | 60 | 80 |
| 240 | 4 | 45 | 69 | 84 |
| 250 | 5 | 45 | 73 | 88 |
| 250 | 7 | 30 | 75 | 90 |
| 280 | 7 | 45 | 71 | 86 |
Table 3
| Temperature ℃ | Pressure MPa | Flow L/h | Total efficiency of carbon conversion % | DME selectivity % |
| 220 | 3 | 30 | 56 | 75 |
| 240 | 4 | 45 | 58 | 78 |
| 250 | 5 | 45 | 64 | 82 |
| 250 | 7 | 30 | 72 | 85 |
| 280 | 7 | 45 | 66 | 81 |
Claims (7)
1, a kind of in combination cot the method for catalytic synthesising dimethyl ether, it is characterized in that: said catalysis is synthesized in the built-up type reaction unit and is carried out; To contain CO, CO
2And H
2Unstripped gas at first carry out catalyzed reaction by three-phase slurry bed conversion zone, then reaction product and unreacted unstripped gas are entered the fixed bed reaction section and carry out catalyzed reaction, temperature of reaction is 220～280 ℃, pressure is 3.0～7.0MPa, in the said three-phase slurry bed conversion zone filling inert liquid phase medium and catalyzer, said fixed bed reaction section also filling same catalyzer; Said catalyzer is catalyst for synthesizing copper based methanol and the composite catalyst that improves the molecular sieve composition, and catalyst for synthesizing copper based methanol is (0.4～2.0) with the quality proportioning of improving molecular sieve catalyst: 1; Said inert liquid phase medium is a medical liquid paraffin; Said reaction unit is combined by three-phase slurry bed conversion zone and fixed bed reaction section, in establish heat-exchanger rig, in time remove reaction heat.
2, the method for claim 1 is characterized in that: said unstripped gas is to be raw material with the coal or to be a kind of in the synthetic gas produced of raw material with the Sweet natural gas; When being that synthetic gas that raw material makes is when being raw material with the coal, the copper-based catalysts of combination cot and the mass ratio of modified molecular sieve catalyst are 1, temperature of reaction is 250～280 ℃, and reaction pressure is 5.0～7.0MPa, and the flow of the inlet unstripped gas under the normal conditions is 30～45L/h;
When with the Sweet natural gas being raw material when making synthetic gas and being unstripped gas, the copper-based catalysts of combination cot is 1 with the ratio of the quality of modified molecular sieve catalyst, and temperature of reaction is 250 ℃, and reaction pressure is 7.0MPa, and the flow of the inlet unstripped gas under the normal conditions is 30L/h.
3, the method for claim 1 is characterized in that: unstripped gas enters three-phase slurry bed conversion zone by gas distributor then through being preheating to 80～180 ℃, carries out catalyzed reaction.
4, the method for claim 1, it is characterized in that: catalyst for synthesizing copper based methanol is (0.6～1.5) with the quality proportioning of improving molecular sieve catalyst: 1, the granularity of catalyzer is 0.1～0.2mm in three-phase slurry bed, and the granularity of catalyzer is φ 5mm * 5mm in fixed bed.
5, the method for claim 1 is characterized in that: the unstripped gas gas space velocity is 1000～15000h
-1
6, the method for claim 1, it is characterized in that: said three-phase slurry bed conversion zone is tower or tank reactor, said fixed bed reaction section is a tower reactor, both are combined into the reactor of an integral body, also can distinguish independent setting, couple together the fixed-bed reactor of promptly connecting behind the triphase slurry bed reactor then with pipeline; The volume ratio of three-phase slurry bed conversion zone and fixed bed reaction section is 10: 3.5.
7, the method for claim 1 is characterized in that: said combination cot reactor comprises shell of reactor (1), interchanger (5), gas distributor (8) and drum (12); Interchanger (5) is arranged in the combination cot reactor, and gas distributor (8) is arranged on the bottom of reactor, and separator (10) is arranged between three-phase slurry bed (2) and the fixed bed (6), and drum (12) is connected with interchanger (5) by pipeline; At three-phase slurry bed (2) built-in inert liquid phase mediums (9) and catalyzer (3), unstripped gas enters in three-phase slurry bed (2) with bubble (4) form by gas distributor (8), at fixed bed (6) apparatus with catalyst inside (7) on sieve plate (11).
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|---|---|---|---|
| CN 02136724 CN1202061C (en) | 2002-08-29 | 2002-08-29 | Method for catalytic synthesising dimethyl ether in combined bed |
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|---|---|---|---|
| CN 02136724 CN1202061C (en) | 2002-08-29 | 2002-08-29 | Method for catalytic synthesising dimethyl ether in combined bed |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8779014B2 (en) | 2006-12-14 | 2014-07-15 | Taiyuan University Of Technology | Slurry catalyst and the preparation thereof |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386138C (en) * | 2003-12-06 | 2008-05-07 | 杭州林达化工科技有限公司 | Process and equipment for internal heat exchanging catalytic reaction |
| EP2898943B1 (en) | 2014-01-28 | 2016-11-16 | Linde Aktiengesellschaft | Process and apparatus for the obtention of dimethylether from syngas |
| CN108262055B (en) * | 2016-12-30 | 2021-03-12 | 中国科学院上海高等研究院 | Catalyst for preparing hydrocarbons by one-step hydrogenation of carbon dioxide and preparation method thereof |
-
2002
- 2002-08-29 CN CN 02136724 patent/CN1202061C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8779014B2 (en) | 2006-12-14 | 2014-07-15 | Taiyuan University Of Technology | Slurry catalyst and the preparation thereof |
| CN110183300A (en) * | 2019-05-08 | 2019-08-30 | 国家能源投资集团有限责任公司 | A kind of process and system by the highly selective propylene processed of synthesis gas |
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